Dendrigraft with citric acid on acrylonitrile/acrylic acid copolymer electrospun fibres

Acrylonitrile/acrylic acid copolymers were synthesized with different mole fractions (1, 2, 5 and 10 mol%) of acrylic acid (AA) in the feed by aqueous suspension polymerization, and bead‐free fibres (295–375 nm in diameter) were made from the copolymers in dimethylformamide solutions by electrospinning. In a heterogeneous system containing electrospun fibre mats, dendritic molecules were grown by reaction between carboxylic acid of AA and –OH groups of citric acid activated by dicyclohexylcarbodiimide. The products were analysed using ¹H NMR, ¹³C NMR and Fourier transform infrared spectroscopies, density determination, scanning electron microscopy, optical microscopy, differential scanning calorimetry and pH response properties. With decreasing AA content, the isotacticity of the copolymers decreases with a more random distribution of the co‐monomers which leads to higher percentage conversions of dendrigraft due to reduced steric hindrance. On the formation of dendrigraft, the percentage conversion of the reactions decreases with an increase of generation number and AA content. A reduction of density for the first generation and then an increase with increasing generation are observed. During oxidation stabilization of fibres with a decrease of AA content and an increase in generation number, the amount of liberated heat increases. Fibres containing more carboxylic groups show significantly greater amounts of swelling/de‐swelling in basic and acidic media, respectively. To be used as nanocarbon fibre precursors, or as active particles for loading with guest molecules, or as pH actuators, the first generation of dendrigrafted fibres are expected to have the greatest potential among the various samples examined. © 2013 Society of Chemical Industry     

Encapsulation of metallo-porphyrins into water-soluble amphipatic dendrigrafts

Newly prepared water-soluble amphipatic hyperbranched organic polymers are used as nanocontainer and as carriers for large metal-organic molecules such as metallo-porphyrins. The hydrosoluble dendrigrafts are constituted by a polystyrene hydrophobic core surrounded by a polyvinyl ether hydrophilic shell. These nanometer-sized amphipatic macromolecules with an average diameter of about 100 nm and narrow polydispersity are fully soluble in aqueous media.Their capacity to encapsulate and transport metallo-porphyrins in aqueous media is investigated. Complexation studies show that up to several thousands of guest molecules can be embedded into each amphipatic dendrigraft macromolecule.     

Dendrigraft polystyrene initiated by poly(p-chloromethyl styrene): synthesis and properties

Dendrigraft polystyrene was prepared using poly(p-chloromethyl styrene) as the multicentre initiator by atom transfer radical polymerization (ATRP). The resulting polymer was characterized with light scattering, intrinsic viscosity, thermal analysis and atomic force microscopy (AFM) imaging. The AFM image showed there were two kinds of different structural dendrigraft polystyrenes in the product, ie the ‘coupling’ dendrigraft polystyrene and ‘free’ dendrigraft polystyrene. The ‘coupling’ structure might result from the coupling reaction of growing radical chain ends. The second virial coefficient A₂ and intrinsic viscosity of the dendrigraft polystyrene were smaller than those of the relative linear and twelve-arm star polystyrene, and the thermal analysis showed that the initial decomposition temperature was a little higher than that of linear polystyrene. © 1999 Society of Chemical Industry     

Copolymer of acrylonitrile/acrylic acid solid surface film dendrigrafted with citric acid

BACKGROUND: The aim of the present work was to improve the properties of acrylic polymer, which is a major fibre‐forming polymer. Acrylonitrile/acrylic acid copolymer, P(AN/AA), was chosen for this purpose and it was intended to study the condition for the formation of hydroxyl groups through the formation of hyperbranched polymers. RESULTS: The synthesis of a dendritic polymer of citric acid (CA) in the solid phase on a P(AN/AA) core is described. The product was analysed using the elemental analysis technique and ¹H NMR. Dendritic molecules were grown by a reaction between the carboxylic acid of acrylic acid and hydroxyl group of CA activated by dicyclohexylcarbodiimide. Products were analysed using Fourier transform infrared and NMR spectroscopy. CONCLUSION: The formation of CA dendrigraft on P(AN/AA) films in a heterogeneous system is possible. The percentage conversion of the copolymer reaction with CA was calculated based on the NMR results. The percentage conversion showed a gradual reduction with an increase in step numbers. The contact angle of water on the films was affected by the percentage conversion of the reactions. A calculation scheme is presented to show that the low degree of conversion leads to an increase in hydrophobic groups. Copyright © 2008 Society of Chemical Industry